Poly(2,6-dimethyl-1,4-phenylene-oxide) derivatives with sulfonyl pendant groups and methods therefor

ABSTRACT

A sulfonyl-substituted polyphenylene-ether polymer having improved dielectric properties and methods for making the same. The sulfonyl-substituted PPE include sulfone-containing polyphenylene oxides (“PPO”) polymers having repeating units of the formulas: 
                         
wherein each of R 1  and R 2  is H or an alkyl group containing from 1 to 4 carbon atoms, R 3  is an alkylene group containing from 1 or 2 carbon atoms, R 4  is selected from a group consisting of an alkyl group containing from 1 to 4 carbon atoms, an aryl group, and CF 3 , and X is a halogen atom. The subscript n is 0 or 1; the subscript m is 1 or 2, provided that when m is 2, R 2  is H. A degree of polymerization ranges from about 5 to about 1,000, and a ratio of units having formula (1) to units having formula (2) of the sulfone-containing PPO polymer ranges from about 10:90 to about 90:10.

RIGHTS OF THE GOVERNMENT

The invention described herein may be manufactured and used by or forthe Government of the United States for all governmental purposeswithout the payment of any royalty.

FIELD OF THE INVENTION

The present invention is directed to sulfonyl-substitutedpoly(phenylene-ether)s having improved dielectric properties and tomethods for making the same.

BACKGROUND OF THE INVENTION

High dielectric constant or permittivity, “high-k,” materials havereceived increasing interest recently for various potential applicationsincluding high energy-density-storage capacitor, gate dielectrics, andelectroactive materials. In particular, high temperature polymers (thosehaving a melting point greater than 150° C.) with high dielectricconstant and low dielectric loss are critical as embedded capacitors,which enable microelectronic-system integration to reduce size withoutcompromising performance or, better still, with the possibility ofenhanced performance in electronic systems. High-k materials suitablefor some applications, such as film capacitors for power-conditioning,power electronics in hybrid electric vehicles, pulsed power, and gatedielectric field-effect transistors, must possess processability, gooddielectric properties over a broad frequency range, and be thermallystable. It is conventionally believed that no single material is able tosatisfy all the above-mentioned prerequisites. Therefore, recent yearshave witnessed an extensive exploitation of polymer-nanocompositestrategies. The overarching goal of these efforts has been to combinethe best characteristics of nanofillers with polymer substrates in asynergistic fashion to improve dielectric performance of the compositematerials by maximizing the dielectric constant while managing thedielectric loss to an acceptable level. From the material sciencestandpoint, there is clearly an increasing need for high-k,nonconducting polymers (i.e., devoid of both intrinsically electronicand ionic conduction) that are processible and compatible with high-knanoparticles.

Poly(phenylene ether)s or “PPEs” are a family of high performancethermoplastics with good high temperature properties and excellenthydrolytic stability. An important member of the PPEs family,poly(2,6-dimethyl-1,4-phenylene oxide), commonly known as PPO, is auseful material that is commercially produced on a large scale. PPO maybe prepared by an oxidative coupling polymerization of2,6-dimethylphenol as shown below:

wherein DP is a degree of polymerization.

PPEs have been considered for low-k materials for the next generation ofmicroelectronic devices because of excellent dielectric properties. Forexample, the dielectric constant, ε_(r), of PPEs ranges between 2.4 and2.6 and tan δ ranges between 0.002 and 0.003 (at 5 GHz for PPO). PPEsalso have a low moisture absorption and are highly resistive to acidsand bases. On the other hand, for these thermoplastics to be attractiveas high-k dielectrics in semiconductor manufacturing processes andenergy-density storage applications, the ε_(r) value would need to besubstantially higher (i.e., greater than 6.0) and tan δ would need to beless than 1%.

Attempts to modify PPEs to achieve the foregoing properties usingconventional methods often yields undesirable cross-linking, requires amulti-step process, or both, such that conventional methods cannot beused for producing polymers having a high degree of functionality. Forexample, Br-PPO reacting with sodium thiomethoxide (methylthiolate) viaa nucleophilic substitution reaction according to convention methodsaffords methylsulfido-PPO (“CH₃S-PPO”). Upon subsequent oxidation bym-CPBA, CH₃S-PPO may be quantitatively converted to the sulfonylproduct, CH₃SO₂-PPO. However, under the same reaction conditions,Br-PPOs having a higher degree of Br-functionalization (greater than 25mol %) fails to convert to the CH₃S-PPO product because of extensive gelformation during the reaction. While wishing to not be bound by theory,it is believed that as an effective concentration of benzylbromide inBr-PPO is increased, the CH₃S— pendant reacted faster thanmethylthiolate nucleophile with the nearby CH₂—Br pendant, resulting ingelation of the polymerization mixture via the formation of sulfoniumsalt crosslinks, which is shown below:

Thus, there remains a need for polymers having suitable dielectricconstants that facilitate microelectronic device manufacture andoperation and improved methods for making these polymers.

SUMMARY OF THE INVENTION

The present invention overcomes the foregoing problems and othershortcomings, drawbacks, and challenges of conventional PPEs byproviding methods for synthesizing PPEs having higher dielectricconstants and lower tan δ properties. While the invention will bedescribed in connection with certain embodiments, it will be understoodthat the invention is not limited to these embodiments. To the contrary,this invention includes all alternatives, modifications, and equivalentsas may be included within the spirit and scope of the present invention.

According to some embodiments of the present invention, asulfonyl-substituted PPE having improved dielectric properties includessulfone-containing PPO having repeating units of the formulae:

wherein each of R¹ and R² is H or an alkyl group containing from 1 to 4carbon atoms, R³ is an alkylene group containing from 1 or 2 carbonatoms, R⁴ is selected from an alkyl group containing from 1 to 4 carbonatoms, an aryl group, and CF₃, X is a halogen atom, the subscript n is 0or 1, the subscript m is 1 or 2 (provided that when m is 2 then R² isH), the degree of polymerization ranges from about 5 to about 1,000, anda mole ratio of units having formula (1) to units having formula (2)ranges from about 10:90 to about 90:10.

Yet other embodiments of the present invention are directed to a methodfor synthesizing a sulfone-containing PPO and includes reacting adi-alkyl-substituted polyphenylene oxide polymer with a halogenatingagent to form a halogenated PPO containing a major amount of halogenatedbenzylic PPO and a minor amount of ring-substituted halogen-containingPPO. The halogenated PPO is then reacted with a sulfinating agent toprovide the sulfone-containing PPO polymer.

In some embodiments of the present invention, X of structure (1) is abromine atom.

In other embodiments, R¹ and R² are selected from —CH₃ and —CH₂CH₃, R³is selected from —CH₂— and —CH₂CH₂—, and R⁴ is selected from CF₃ and anaryl group.

In some embodiments, the aryl group of R⁴ contains one, two, or threesubstituents selected from —CH₃, —OCH₃, a dimethyl amino group, and adiethylamino group. In other embodiments, the aryl group is apara-substituted aryl group wherein the substituent is selected from ahalide, —CH₃, —OCH₃, a dimethyl amino group, and a diethylamino group.In still other embodiments, the aryl group is an ortho-substituted arylgroup wherein the substituent is selected from a halide, —CH₃, —OCH₃, adimethyl amino group, and a diethylamino group. In yet otherembodiments, the aryl group includes one para-group and two ortho-groupseach selected from a halide, —CH₃, —OCH₃, a dimethyl amino group, and adiethylamino group.

In other embodiments, the amount of halogen-containing units in thepolymer ranges from about 0.20 mol % to about 0.40 mol %.

In some embodiments, the units of formula (1) of the sulfone containingpolymer include units of the formulas:

wherein a molar ratio of units of formula (3) to units of formula (4)ranges from about 64:36 to about 99:1.

In other embodiments, the units of formula (2) include units offormulas:

wherein a molar ratio of units of formula (5) to units of formula (6)ranges from about 1:0 to about 5:3.

In other embodiments, the halogenating agent may be selected fromelemental bromine and a brominated imide compound. In some embodiments,the halogenating agent is bromo-succinimide in admixture withazo-bis(isobutyronitrile). In other embodiments, a mole ratio ofdi-alkyl-substituted PPO to brominating agent ranges from about 1.0:0.5to about 1.0:3.0.

In some embodiments, the sulfinating agent is selected from sodiummethane sulfinate. In other embodiments, a mole ratio of sodium methanesulfonate salt to halogenated PPO ranges from about 1.0:1.0 to about3.0:1.0. In still other embodiments, the sulfinating agent may beselected from but not limited to, the following alkaline salts oftrifluoromethanesulfinate, benzenesulfinate, 4-fluorophenylsulfinate,4-toluenesulfinate, 4-methoxyphenylsulfinate, and4-dimethylamino-phenylsulfinate.

Other embodiments include a method for synthesizing a sulfone-containingPPO by reacting a di-alkyl-substituted PPO with a halogenating agent toform a halogenated PPO having a halogenated benzylic PPO content and aring-substituted halogen-containing PPO content that is less than thehalogenated benzylic PPO content. The halogenated PPO content is reactedwith a sulfinating agent to provide the sulfone-containing PPO, whereinthe polymer includes from about 10 mol % to about 90 mol % sulfonylgroups.

According to embodiments of the present invention, compositions andmethods of preparation for a series of high dielectric constant andrelatively low loss derivative polymers derived frompoly(2,6-dimethyl-1,4-phenylene oxide) containing variable amounts ofhighly polar sulfonyl pendants exemplified by methylsulfonyl (CH₃SO₂—),trifluoromethylsulfonyl (CF₃SO₂—), phenylsulfonyl (PhSO₂—), and4-fluorophenylsulfonyl (4-FC₆H₄SO₂) moieties are described. Theforegoing PPE derivatives are potentially useful as neat polymer filmsmatrix polymers or polymer substrates for electronic applications wherehigh permittivity and low dielectric loss are desired such as polymerphotovoltaics, flexible electronics, polymer capacitors, highenergy-density hybrid capacitors, and the like, as well as coatings forelectromagnetic shielding applications.

Additional objects, advantages, and novel features of the invention willbe set forth in part in the description which follows, and in part willbecome apparent to those skilled in the art upon examination of thefollowing or may be learned by practice of the invention. The objectsand advantages of the invention may be realized and attained by means ofthe instrumentalities and combinations particularly pointed out in theappended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings, which are incorporated in and constitute apart of this specification, illustrate embodiments of the presentinvention and, together with a general description of the inventiongiven above, and the detailed description of the embodiments givenbelow, serve to explain the principles of the present invention.

FIG. 1A is a H-NMR spectrum (taken in CDCl₃) of a sulfone-containing,Br-PPO synthesized in a carbon tetrachloride solvent according toembodiments of the present invention.

FIG. 1B is a H-NMR spectrum (taken in CDCl₃) of a sulfone-containing,Br-PPO synthesized in a phenyl chloride solvent according to embodimentsof the present invention.

FIG. 1C is a H-NMR spectrum (taken in CDCl₃) of a sulfone-containing,Br-PPO synthesized in a tetrachloroethane solvent according toembodiments of the present invention.

FIG. 2A is a H-NMR spectrum of sulfone-containing PPO in a reactionmixture of benzyl bromide, wherein signals denoted with an asterisk, *,are due to protio residues of deuterated dimethyl sulfoxide (“DMSO-d₆”).

FIG. 2B is a H-NMR spectrum of sulfone-containing PPO in a reactionmixture of benzyl bromide and (methylsulfonylmethyl)benzene, whereinsignals denoted by * are due to protio residues of DMSO-d₆.

FIGS. 3A-3C are H-NMR spectra of Br-PPO, CH₃S-PPO, and CH₃SO₂-PPO inDMSO-d₆, respectively.

FIG. 4A graphically illustrates temperature-dependent effects on adielectric constant for 25 mol % CH₃SO₂-PPO film prepared in accordancewith an embodiment of the present invention.

FIG. 4B graphically illustrates temperature-dependent effects ondielectric loss for 25 mol % CH₃SO₂-PPO film prepared in accordance withan embodiment of the present invention

FIGS. 5A-5B graphically illustrate a D-E hysteresis loop for the 25 mol% CH₃SO₂-PPO film of FIGS. 4A and 4B.

FIGS. 6A-6B graphically illustrate a D-E hysteresis loop for 50 mol %CH₃SO₂-PPO film prepared in accordance with an embodiment of the presentinvention.

It should be understood that the appended drawings are not necessarilyto scale, presenting a somewhat simplified representation of variousfeatures illustrative of the basic principles of the invention. Thespecific design features of the sequence of operations as disclosedherein, including, for example, specific dimensions, orientations,locations, and shapes of various illustrated components, will bedetermined in part by the particular intended application and useenvironment. Certain features of the illustrated embodiments have beenenlarged or distorted relative to others to facilitate visualization andclear understanding. In particular, thin features may be thickened, forexample, for clarity or illustration.

DETAILED DESCRIPTION OF THE INVENTION

Embodiments of the present invention provide sulfonyl-substitutedpoly(phenylene ether)s (“PPEs”) having improved dielectric propertiesand methods of synthesizing the same. According to an exemplaryembodiment, polyphenylene oxide generally, orpoly(2,6-dimethyl-1,4-phenylene oxide) (“PPO”) specifically, is astarting material for making the sulfonyl-substituted PPEs describedherein.

As can be seen from the PPO structure, below, the nature of sitesavailable for chemical modification, namely the polymer backbone, methylpendant groups, and endgroups, may be considered aromatic (sp²C—H),aliphatic (sp³C—H), and protic (O—H), in that order.

Organic and organometallic reactions may be used as specific tools tointroduce functional groups into the polymer corresponding to thechemical nature of the sites. Thus, aromatic electrophilic substitutionreactions (such as nitration, halogenation, Friedel-Crafts acylation andsulfonylation, and sulfonation) may be used to generate PPO derivativeswith aromatic nitro, halide, or sulfonic acid, respectively. Freeradical halogenation with chlorine or bromine at higher temperatures orunder irradiation may be used to react with the —CH₃ pendant groups. Theresulting PPO derivative having benzylic halogens may subsequently bereacted with a variety of N, O, S, or P nucleophiles to form neutralpendants or quarternized with tertiary amines. Metalation of alkylsubstituted polyethers with organolithium compounds occurs initially onthe nucleus and, on standing or at higher temperatures, transfers to thependant alkyl group via Li—H exchange. However, with organo-sodium orpotassium reagents, metalation occurs exclusively on the alkyl group.The metalated PPO derivatives will react as polymeric initiators foranionic polymerization of various vinyl monomers, organotrisiloxanes,and phenyl isocyantes.

According to one embodiment of the present invention, a chemicaltransformation may be used to structurally modify PPO, for example,radical halogenation (more specifically as applied to some embodiments,bromination) which may be the most ubiquitous method used because of theease in operation and scalability of the reaction. The resultinghalogenated PPO (“X-PPO,” where X is the halogen) is a versatileintermediate for introducing a wide range of functional groups to impartdesired final properties (such as chemical resistance and higher thermalstability) without the risk of molecular weight reduction and thepossibility of converting the linear architecture of PPO to that of anetwork.

According to one specific embodiment of the present invention, PPO maybe brominated with bromine in 1,1,2,2-tetrachloroethane (“TCE”) and mayyield two bromine atoms per repeat unit and a substantial amount ofaromatic bromination:

wherein x is a mole fraction of unreacted PPO units, y is a molefraction of benzyl brominated units, z is a mole fraction of phenylbrominated units, and the subscript n is a number of repeat unites inthe Br-PPO. The mole fractions of x, y, and z are such that x+y+z=1.

For synthesis of a sulfonyl-substituted PPO according to an embodimentof the present invention, halogenation may proceed with or without asuitable halogenation agent, which is, at least partially, dependent onthe halogen to be introduced. In accordance with one particularembodiment of the present invention, PPO may be brominated with bromineor N-bromosuccinimide (“NBS”). Reaction parameters considered mayinclude: (i) type of brominating reagents (Br₂ versusNBS/azo-2,2′-isobutyronitrile (“ARM”) and NBS/benzoyl peroxide (“BPO”),(ii) a stoichiometry of the brominating agent to the repeat unit of PPO;(iii) chlorinated solvents of varied dipole moments, (iv) temperatures,and (v) reaction times. A reaction sequence with NBS/AIBN in twodifferent solvents and at various temperatures may include:

By following an appropriate combination of the reaction parameters(i)-(v), benzyl bromination ranging from 10 mol % to 80 mol %, or more,may be achieved in Br-PPO. This range of benzyl bromination may beconsidered as a range for the degree of functionalization resulting fromthe subsequent reaction to displace bromide in Br-PPO.

In order to synthesize high dielectric constant polymers, nonpolarmethyl pendants may be converted to highly polar groups, such as—CH₂SO₂Me, —CH₂SO₂CF₃, and the like. The high polarity of the foregoinggroups is expected to derive from the high polarity exhibited by theparent molecules, namely, dimethyl sulfone (CH₃SO₂Me, dipole moment,4.44±0.1 D, gas phase; 4.25 D); methyl trifluoromethylsulfone(CH₃SO₂CF₃; dipole moment 3.74 D); and phenyl methyl sulfone (CH₃SO₂Ph;dipole moment 4.8 D), which are expected to contribute to the enhanceddielectric constant and acceptable dielectric loss of sulfonyl-PPO.

The PPO pendant may be converted from benzyl bromide to benzylsulfonyl(“Bz-SO₂R”) using a two-step process. At start, there may be anucleophilic displacement reaction with an appropriate alkylthiolate,which may then be followed by oxidation of the sulfide intermediate to asulfone product with an appropriate oxidizing agent (such as hydrogenperoxide, sodium periodate, m-chloroperbenzoic acid (“m-CPBA”), etc.).

To circumvent the problem of crosslinking that occurs with conventionalmethods, and particularly when Br-PPO has a degree of functionalizationof greater than 25%, the tandem nucleophilic character of themethylsulfido pendant was eliminated by masking or blocking its secondreactivity, according to a specific embodiment of the present invention.More particularly, Br-PPO may be converted to RSO₂-PPO by nucleophilicsubstitution reaction of the benzylbromo pendants of Br-PPO by sodiumorganosulfinate salt in a polar aprotic solvent, such asN,N′-dimethylacetamide (“DMAc”), at room temperature. Such reaction isillustrated below:

The illustrative method may be used to achieve any degree ofRSO₂-functionalization ranging from about 10 mol % to about 80 mol %, ormore.

The following examples illustrate particular properties and advantagesof some of the embodiments of the present invention. Furthermore, theseare examples of reduction to practice of the present invention andconfirmation that the principles described in the present invention aretherefore valid but should not be construed as in any way limiting thescope of the invention.

Example 1—Bromination of PPO Via NBS and AIBN

(BR-PPO with 25.1 mol % Functionality)

Commercial PPO (4.80 g, 40.0 mmol) and CCl₄ (100 mL) were added to a 500mL, 3-necked flask equipped with a magnetic stirrer, a nitrogen inlet,and an outlet, and stirred under dry nitrogen at 50° C. until PPO wasdissolved. NBS (3.56 g, 20.0 mmol) and AIBN (0.32 g) were then placed inthe flask. The mixture was heated under reflux for 1 hr. The viscoussolution was diluted with CCl₄ and precipitated into methanol to affordwhite fibers, which was collected by filtration. The product was driedin an oven and provided 5.60 g (88%) of light brown fibers. The ATR-IRpeak values (cm⁻¹) were: 3036, 2973, 2918, 2860, 1603, 1462, 1305, 1188,1028, 986, 964, 860, 827, 637, 590, 504.

Example 2—Bromination of PPO with NBS and AIBN

(BR-PPO with 33.9 mol % Functionality).

Commercial PPO (4.80 g, 40.0 mmol), CCl₄ (100 mL), NBS (7.12 g, 40.0mmol), and AIBN (0.32 g) were used in a process similar to Example 1,except the mixture was heated under reflux for 2 hr. The product wasdried in oven and provided 6.10 g (88%) of light brown fibers (FIG. 1A).The ATR-IR peak values (cm⁻¹) were: 3035, 2973, 2918, 2860, 1603, 1464,1305, 1187, 1028, 986, 964, 860, 827, 637, 590, 504.

Example 3—Bromination of PPO with NBS and AIBN

(BR-PPO with 40.7 mol % Functionality).

Commercial PPO (4.80 g, 40.0 mmol), CCl₄ (100 mL), NBS (7.12 g, 40.0mmol) and AIBN (0.32 g) were used in a process similar to Example 1,except the mixture was heated under reflux for 3 hr. The yield was 6.2 g(85%). The ATR-IR peak values (cm⁻¹) were: 3035, 2980, 2918, 1603, 1464,1305, 1219, 1189, 1030, 986, 862, 825, 629, 589, 503. Anal. Calc. (%).for C₈H_(7.18)Br_(0.82)O: C, 51.98; H, 3.92; Br, 35.44. Found: C, 51.71;H, 3.81; Br, 35.35.

Example 4—Bromination of PPO with NBS and AIBN

(BR-PPO with 52.0 mol % Functionality).

Commercial PPO (4.80 g, 40.0 mmol), CCl₄ (200 mL), NBS (12.82 g, 72.0mmol), and AIBN (0.32 g) were used in a process similar to Example 3.The mixture was heated under reflux for 3 hr to provide 6.4 g (79%) offibers. The ATR-IR peak values (cm⁻¹) were: 3036, 2981, 2918, 1603,1464, 1305, 1219, 1190, 1030, 986, 862, 826, 629, 589, 503. Anal. Calc(%). for C₈H_(6.94)Br_(1.06)O: C, 47.14; H, 3.44; Br, 41.56. Found: C,46.86; H, 3.21; Br, 41.72.

Example 5—Bromination of PPO with NBS and AIBN (BR-PPO)

Commercial PPO (4.80 g, 40.0 mmol), CCl₄ (300 mL), NBS (17.09 g, 96.0mmol), and AIBN (0.32 g) were used in a process similar to Example 1.After the mixture was heated under reflux for 1 hr, a gel formed andbecame insoluble in any solvent.

Example 6—Bromination of PPO with NBS and AIBN

(BR-PPO with 79.2 mol % Functionality).

Commercial PPO (4.80 g, 40.0 mmol), chlorobenzene (266 mL), NBS (16.64g, 93.4 mmol), and AIBN (0.32 g) were used. The mixture was heated underreflux for 24 hours to provide 9.30 g (95%) of fibers. The ATR-IR peakvalues (cm⁻¹) were: 3029, 2975, 1601, 1454, 1303, 1216, 1190, 1030, 994,865, 794, 627, 575, 509. Anal. Calc. (%) for C₈H_(6.41)Br_(1.59)O: C,39.10; H, 2.64; Br, 51.72. Found: C, 39.01; H, 2.56; Br, 52.47.

Example 7—Bromination of PPO with NBS and AIBN

(BR-PPO with 80.1 mol % Functionality).

Commercial PPO (4.80 g, 40.0 mmol), chlorobenzene (266 mL), NBS (21.36g, 120 mmol), and AIBN (0.32 g) were used. The mixture was heated underreflux for 24 hr to provide 9.60 g (98%) of fibers. (Example 7 in FIG.1B). The ATR-IR peak values (cm⁻¹) were: 3036, 2975, 1602, 1455, 1304,1191, 1030, 995, 866, 793, 669, 628, 576, 509.

Example 8—Bromination of PPO with NBS and AIBN

(BR-PPO with 19.2 mol % Functionality).

Commercial PPO (4.80 g, 40.0 mmol), CHCl₃ (100 mL), NBS (7.12 g, 40.0mmol), and AIBN (0.32 g) were used in a process similar to Example 3.The mixture was heated under reflux for 3 hr to afford 5.3 g (82%) offibers. The ATR-IR peak values (cm⁻¹) were: 3036, 2922, 2917, 1601,1464, 1305, 1219, 1190, 1189, 1022, 986, 862, 826, 634, 586.

Example 9—Bromination of PPO with NBS and BPO

(BR-PPO with 9.94 mol % Functionality).

Commercial PPO (4.80 g, 40.0 mmol), 1,2-dichloroethane (100 mL), NBS(7.12 g, 40 mmol), and benzyl peroxide (BPO) (0.48 g) were used in aprocess similar to Example 3. The mixture was heated at 70° C. for 3 hrto afford 5.90 g (91%) of fibers. The ATR-IR peak values (cm⁻¹) were:3036, 2953, 2919, 1602, 1468, 1424, 1379, 1305, 1183, 1115, 1019, 958,854, 825, 777, 754, 594, 563.

Example 10—Bromination of PPO with Elemental Bromine

(BR-PPO with 21.9 mol % Benzylbromide).

Commercial PPO (4.80 g, 40.0 mmol) and 1,1,2,2-tetrachloroethane (100mL) were added to a 500 mL, 3-necked flask equipped with a magneticstirrer, a nitrogen inlet, and an outlet, and stirred under dry nitrogenat 50° C. until PPO was dissolved. Then Br₂ (3.52 g, 44.0 mmol) wasadded slowly under reflux for 3 hr. The viscous solution wasprecipitated into methanol to afford white fibers, which were collectedby filtration. The product was dried in oven to provide 7.40 g (97%) oflight brown fibers. NMR spectra is shown in FIG. 1C. The ATR-IR peakvalues (cm⁻¹) were: 3035, 2954, 2921, 1600, 1462, 1400, 1380, 1306,1188, 1022, 986, 963, 857, 791, 670, 631, 590.

Example 11—Bromination of PPO with 37.7 mol % Benzylbromide

Commercial PPO (4.80 g, 40.0 mmol), Br₂ (6.40 g, 80.0 mmol), and1,1,2,2-tetrachloroethane (100 mL) were used. The mixture was heatedunder refluxing for 3 hr to afford 7.4 g (96%) of light brown fibers.The ATR-IR peak values (cm⁻¹) were: 3035, 2954, 2921, 1600, 1462, 1400,1380, 1306, 1188, 1022, 986, 963, 857, 791, 670, 631, 590.

Table 1, below, is a summary of the reaction conditions and results forthe above bromination examples.

TABLE 1 PPO BROMINATION CONDITIONS AND PERCENTAGE OF BR-PPO PRODUCTSExample Bromination Molar Reaction Reaction Reaction Mol % of Mol % ofMol % No. Reagent Ratio¹ Solvent Temp. (° C.) Time (hr) Methyl-Br²Aryl-Br² Unreacted PPO 1 NBS/AIBN  1:0.5 CCl₄ 88 2 25.1 0.24 74.7 2NBS/AIBN 1:1 CCl₄ 88 2 33.9 0.45 65.7 3 NBS/AIBN 1:1 CCl₄ 88 3 40.7 0.6258.7 4 NBS/AIBN  1:1.8 CCl₄ 88 3 52.0 1.60 46.4 5 NBS/AIBN  1:2.4 CCl₄88 1 ³ ³ ³ 6 NBS/AIBN   1:2.33 Chlorobenzene 145 24 79.2 0.45 20.4 7NBS/AIBN 1:3 Chlorobenzene 145 24 80.1 0.42 19.5 8 NBS/AIBN 1:1 CHCl₃ 803 19.2 6.67 74.1 9 NBS/BPO 1:1 CH₂ClCH₂Cl 70 3  9.94 32.3 57.8 10 Br₂ 1:1.1 CHCl₂CHCl₂ 130 3 21.9 13.6 64.5 11 Br₂ 1:2 CHCl₂CHCl₂ 130 3 37.716.3 46.0 wherein ¹the molar ratio is bromination agent to PPO, ²the mol% of Methyl-Br and mol % of Aryl-Br were calculated from NMR spectra(FIGS. 1A-1C) and in accordance with the Equations 1 and 2 (below), and³ gelation occurred in 1 hr and the product became insoluble in anysolvent.

$\begin{matrix}{{{Mol}\mspace{14mu}\%\mspace{14mu}{of}\mspace{14mu}{Methyl}\text{-}{Br}} = \frac{{Intergration}\mspace{14mu}{Value}\mspace{14mu}{of}\mspace{14mu}{Peak}\mspace{14mu} 2}{\begin{matrix}{{{Intergration}\mspace{14mu}{Value}\mspace{14mu}{of}\mspace{14mu}{Peak}\mspace{14mu} 2} +} \\{\left( {{{Intergration}\mspace{14mu}{Values}\mspace{14mu}{of}\mspace{14mu}{Peak}\mspace{14mu} 1} + 3} \right)*\frac{2}{3}}\end{matrix}}} & {{Equation}\mspace{14mu} 1} \\{{{Mol}\mspace{14mu}\%\mspace{14mu}{of}\mspace{14mu}{Ar}\text{-}{Br}} = \frac{\left( {{Intergration}\mspace{14mu}{Value}\mspace{14mu}{of}\mspace{14mu}{Peak}\mspace{14mu} 3} \right)*\frac{2}{3}}{\begin{matrix}{{{Intergration}\mspace{14mu}{Value}\mspace{14mu}{of}\mspace{14mu}{Peak}\mspace{14mu} 2} +} \\{\left( {{{Intergration}\mspace{14mu}{Values}\mspace{14mu}{of}\mspace{14mu}{Peak}\mspace{14mu} 1} + 3} \right)*\frac{2}{3}}\end{matrix}}} & {{Equation}\mspace{14mu} 2}\end{matrix}$

As summarized in Table 1, above, the combination of NBS/AIBN togetherwith nonpolar carbon tetrachloride (CCl₄), commonly used for allylic orbenzylic bromination driven by free-radical chain process, were found tobe effective in minimizing the formation of aryl bromide (Examples 1 to4), based on the quantitative proton NMR comparison as depicted in FIGS.1A-1C. With reference to FIGS. 1A-1C, proton-NMR spectra (CDCl₃) ofGr-PPO in a CCl₄ solvent (FIG. 1A; Example 2), Br-PPO in chlorobenzenesolvent (FIG. 1B; Example 7), and Br-PPO in tetrachloroethylene solvent(FIG. 1C; Example 10) are shown. The characteristic benzylic protonsignals are labeled as 1 for CH₃ ortho to H, 2 for CH₃ ortho to Br(i.e., undesired aromatic PPO repeat unit) and 3 for CH₂Br (i.e., thedesired Br-PPO repeat unit) in FIGS. 1A-1C.

Reaction time is important and, under the conditions described above,should be conducted for no more than 3 hr. After this 3 hr reactiontime, Br-PPO starts to precipitate out and form an insoluble gel if thereaction is allowed to continue after the first sign of precipitation(Example 5). Because of this constraint, the highest percentage ofbromine on methyl group is 52.0 mol % when CCl₄ was used as the solvent.Thus, to keep the Br-PPO in solution, chlorobenzene with greatersolvating power was used and, indeed, the percentage of bromine on themethyl group was raised to about 80 mol % (Examples 6 and 7).

Functionalization of Br-PPO with a polar group is illustrated by thefollowing examples.

Example 12—Preparation of Thiomethoxide-PPO

(CH₃S-PPO with 25.1 mol % Benzylsulfide).

Br-PPO (Example 1: 1.59 g, 10.0 mmol) and dimethylacetamide (“DMAc”) (50mL) were added to a 250 mL, 3-necked flask equipped with a magneticstirrer, a nitrogen inlet, and an outlet, and stirred under dry nitrogenat room temperature until Br-PPO was dissolved to form a yellowsolution. Then, the sodium salt of methane sulfinic acid (0.35 g, 5.0mmol) was added slowly. The mixture was agitated overnight at roomtemperature and poured into methanol. The white powder was collected byfiltration and dried in an oven to afford 1.34 g (94%) of product. TheATR-IR peak values (cm⁻¹) were: 2982, 2971, 2917, 1598, 1460, 1420,1397, 1381, 1304, 1183, 1021, 992, 958, 852.

Example 13—Preparation of Methylsulfonyl-PPO

(CH₃SO₂-PPO with 25.1 mol % Functionality).

Oxidation of methylsulfide pendants by meta-chloropeoxybenzoic acid:CH₃S-PPO (Example 12: 1.0 g, 7.0 mmol) and CHCl₃ (40 mL) were added to a100 mL, 3-necked flask equipped with a magnetic stirrer, a nitrogeninlet, and an outlet, and stirred under dry nitrogen at room temperatureuntil Br-PPO was dissolved. Then the flask was cooled to 0° C. andmeta-chloroperoxybenzoic acid (mCPBA, 1.8 g, 8.0 mmol) was added slowly.After the addition of mCPBA, a temperature of the reaction mixture wasallowed to rise to room temperature for 2 hr, and the mixture wasprecipitated into methanol. The white precipitate was collected anddried in a vacuum oven to provide 0.94 g (84%) of product. The ATR-IRpeak values (cm⁻¹) were: 2981, 2929, 2886, 1600, 1462, 1422, 1398, 1382,1303, 1251, 1186, 1158, 1118, 1022, 989, 959, 887, 857, 752, 527, 491,449.

For the direct substitution of benzylbromide pendants bymethanesulfinate nucleophile, Br-PPO (Example 1; 1.50 g, 9.40 mmol) andDMAc (20 mL) were added to a 100 mL, 3-necked flask equipped with amagnetic stirrer, a nitrogen inlet, and an outlet, and stirred under drynitrogen at room temperature until Br-PPO was dissolved. Then sodiummethanesulfinate (0.75 g, 7.3 mmol) was added to the mixture in theflask. The mixture was agitated overnight at room temperature and pouredinto water/methanol co-solvent (1:1). The off-white solid was collectedby filtration and dried in a vacuum oven to provide 1.38 g (92%) ofproduct. The ATR-IR peak values (cm⁻¹) were: 2981, 2929, 2886, 1600,1462, 1422, 1398, 1382, 1303, 1251, 1186, 1158, 1118, 1022, 989, 959,887, 857, 752, 527, 491, 449.

Example 14—Preparation of Thiomethoxide-PPO

(CH₃S-PPO with 33.9 mol % Functionality).

Following the procedure described in Example 12, Br-PPO (Example 2; 1.73g, 10.0 mmol), methane sodium thiomethoxide (0.45 g, 6.4 mmol), and DMAc(50 mL) were used. Gelation occurred overnight.

The foregoing Examples 12 and 13 demonstrate a two-step process forpreparing methylsulfonyl-PPO having at least 25.1 mol % benzylsulfide.However, as shown in Example 14, for benzylsulfide functionality above25 mol %, crosslinking and gelation occur. To circumvent the problem ofcrosslinking associated with the conventional methods, the nucleophiliccharacter of the methylsulfido pendant was eliminated by masking orblocking its reactivity. Because organic sulfinate salts (e.g., RSO₂⁻Na⁺) react easily with alkyl or benzyl halides; the benzyl-sulfonylproduct was preferably achieved by directly converting benzyl bromide tobenzylsulfone by the following reaction:

wherein R is selected from the group consisting of —CH₃, —CF₃, —C₆H₅,—C₆H₄CH₃, and —C₆H₄F, as illustrated, below, in Examples 15-20.

Example 15—Preparation of Methylsulfonyl-PPO

(CH₃SO₂-PPO with 50 mol % Functionality).

Br-PPO (Example 4; 0.50 g, 2.5 mmol) and DMAc (20 mL) were added to a100 mL, 3-necked flask equipped with a magnetic stirrer, a nitrogeninlet, and an outlet, and stirred under dry nitrogen at room temperatureuntil Br-PPO was dissolved. Sodium methanesulfinate (0.32 g, 2.7 mmol)was added to the mixture in the flask. After the mixture was agitated atroom temperature overnight it was poured into water/methanol co-solvent(1:1). The brown solid was collected by filtration and dried in a vacuumoven to provide 0.41 g (82%) of product. The ATR-IR peak values (cm⁻¹)were: 3015, 2930, 1602, 1464, 1301, 1248, 1192, 1160, 1118, 1030, 989,963, 897, 757, 491, 450.

Example 16—Methylsulfonyl-PPO

(CH₃SO₂-PPO with 80 mol % Functionality, 4-3).

Br-PPO (Example 7; 0.50 g, 2.0 mmol), sodium methanesulfinate (0.64 g,5.4 mmol), and DMAc (20 mL) were used in a process similar to Example 15to provide 0.46 g (92%) of a brown powder. The ATR-IR peak values (cm⁻¹)were: 2981, 2930, 1602, 1460, 1405, 1293, 1250, 1194, 1157, 1114, 991,961, 884, 756, 685, 448.

Example 17—Trifluoromethylsulfonyl-PPO

(CF₃SO₂-PPO with 50 mol % Functionality)

Br-PPO (Example 4; 0.50 g, 2.5 mmol), sodium trifluoromethanesulfinate(0.50 g, 3.2 mmol), and DMAc (20 mL) were used in a process similar toExample 15 to provide 0.62 g (98%) of a light-yellow powder. The ATR-IRpeak values (cm⁻¹) were: 2937, 1605, 1369, 1307, 1196, 1119, 1030, 988,870, 769, 729.

Example 18—Benzenesulfonyl-PPO

(C₆H₅SO₂-PPO with 50 mol % Functionality)

Br-PPO (Example 4; 0.50 g, 2.5 mmol), sodium benzenesulfonate (0.85 g,5.2 mmol), and DMAc (20 mL) were used in a process similar to Example 15to provide 0.63 g (97%) of a light-yellow powder. ATR-IR peak values(cm⁻¹) were: 3063, 1606, 1466, 1448, 1307, 1194, 1156, 1132, 1085, 1028,988, 877, 737.

Example 19—4-Toluenesulfonyl-PPO

(P-MEC₆H₄SO₂-PPO (with 50 mol % Functionality)

Br-PPO (Example 4; 0.50 g, 2.5 mmol), sodium 4-toluenesulfonate (0.85 g,4.4 mmol), and DMAc (20 mL) were used in a process similar to Example 15to provide 0.70 g (100%) of a light-yellow powder. The ATR-IR peakvalues (cm⁻¹) were: 2926, 1600, 1465, 1319, 1303, 1245, 1194, 1156,1132, 1087, 1031, 988, 870, 816, 734.

Example 20—4-Fluorobenzenesulfonyl-PPO

(4-FC₆H₅SO₂-PPO with 50 mol % Functionality)

Br-PPO (Example 4; 0.50 g, 2.5 mmol), sodium 4-fluorobenzenesulfonate(0.90 g, 4.9 mmol), and DMAc (20 mL) were used in a process similar toExample 15 to provide 0.63 g (91%) of an off-white powder. The ATR-IRpeak values (cm⁻¹) were: 3074, 2928, 1591, 1493, 1466, 1405, 1322, 1292,1235, 1194, 1152, 1086, 1031, 988, 839, 820, 740.

In order to confirm the feasibility of the procedure used in Examples 15and 16, a proton NMR spectrum of a model compound was obtained. Thebenzyl bromide was treated with sodium methanesulfinate (MeSO₂Na) atroom temperature in DMSO. An instantaneous and clean reaction to produce(methylsulfonylmethyl)benzene was observed. The proton NMR spectrum ofthe reaction mixture, shown in FIG. 2B, indicates the completedisappearance of the starting benzyl bromide benzyl proton signal, theconcomitant appearance of benzyl proton signal of the sulfone product atlower chemical shift, and a new —CH₃ peak. Referring to FIGS. 2A-2B, thespectra of benzyl bromide and reaction mixture of benzyl bromide (FIG.2A) and methylsulfonylmethyl)benzene (FIG. 2B) are shown. Benzyl bromidewas converted into (methylsulfonylmethyl)benzene at room temperature inDMSO-d₆. A small amount of benzyl alcohol (—CH2- at d 3.35 and OH at d4.70, denoted by *) was also formed from the reaction of excess benzylbromide with water present in DMSO-d₆.

Thus, in the similar reaction, chemically modified PPO with a content upto 80 mol % has been successfully prepared by treating Br-PPO withsodium methanesulfinate using DMAc as a solvent. As shown in FIGS.3A-3C, the comparison of the proton NMR spectra of the starting Br-PPOand the isolated CH₃SO₂-PPO, together with the characteristic NMRsignals associated with benzyl bromide and benzylmethylsulfone, hasvalidated the quantitative yield of sulfonyl-PPO. Further, thissynthetic method can be extended to RSO₂Na with R other than methyl,especially R═CF₃ and 4-substituted phenylene (4-XC₆H₄—) for highpermittivity PPO. FIGS. 3A-3C provide the H-NMR spectra of Br-PPO (FIG.3A, spectrum taking in CDCl₃; Example 7), CH₃S-PPO (FIG. 3B, spectrumtaking in CDCl₃; Examples 12 and 13), and CH₃SO₂-PPO (FIG. 3C, spectrumtaking in DMSO-d₆; Example 16). Both Br-PPO and CH₃SO₂-PPO had thedegree of functionalization of 80 mol %. CH₃S-PPO had the degree offunctionalization of 25 mol %.

All of the polymers described herein Example 20, except CH₃SO₂-PPOcontaining 80 mol % functionality, are soluble in CHCl₃, chlorobenzene,tetrahydrofuran (“THF”), DMAc and DMSO. Highly polar CH₃SO₂-PPOcontaining 80 mol % functionality becomes insoluble in solvents withlower polarity, such as CHCl₃.

The molecular weight and polydispersity (“PDI”) of the PPO describedabove were measured by gel-permeation chromatography (“GPC”) in THF at30° C. with a polystyrene standard. A commercially-available PPO sampleexhibited comparable GPC results to a high molecular weight PPO sample(HMW PPO) (Table 2). However, Br-PPO and CH₃S-PPO polymers exhibitedexceptionally high molecular weights (one order of magnitude higher thanthe unmodified PPO) and narrow PDIs (decreasing from 3 to less than 2),which indicates a likelihood that the polymers aggregated in THFsolution. The molecular weight of CH₃SO₂-PPO was only slightly higherthan PPO, as shown in Table 2.

TABLE 2 PPO MOLECULAR WEIGHTS AND POLYDISPERSITY Sample No Sample NameM_(n) M_(w) PDI Commercial PPO-1 36,500 112,000 3.06 PPO-1 CommercialPPO-2 21,700 68,600 3.20 PPO-2 Example 2 Br-PPO (34 mol %) 240,000333,000 1.39 Example 4 Br-PPO (52 mol %) 338,000 466,000 1.38 Example 6Br-PPO (79 mol %) 210,000 304,000 1.52 Example 12 CH₃S-PPO (25 mol %)254,000 469,000 1.84 Example 13 CH₃SO₂-PPO (25 mol %) 247,000 472,0001.91 Example 16 CH₃S-PPO (80 mol %) 61,200 120,000 1.96

The commercially-available PPO possessed a glass transition temperature(“T_(g)”) at 212° C. and good thermal stability under inert atmosphere.Incorporation of bromine (less than 52 mol %) and thiomethoxide resultedin a decrease in the glass transition temperature, Br-PPO andCH₃SO₂-PPO, respectively since the modified side groups would increasethe free volume and impart plasticizing effect. The T_(g) of Br-PPOcontaining 80 mol % of functionality increased to 250° C. since thebulky bromide groups prevent the PPO main chains from rotating freely.T_(g) values for CH₃SO₂-PPOs were equal to or higher than T_(g) valuesof PPO due to the high polarity of side chains, and the thermallystabilities of all were all substantially reduced. A summary of thethermal properties of the PPO is provided in Table 3.

TABLE 3 THERMAL PROPERTIES OF PPO AND ITS DERIVATIVES T_(d5%) ² T_(d5%)² Tg¹ (° C.) (° C.) in Example No. Sample Name (° C.) in air nitrogenCommercial PPO-2 212 390 423 PPO-2 1 Br-PPO 208 281 285 2 Br-PPO 204 277277 4 Br-PPO 201 268 270 6 Br-PPO 250 248 234 12 CH₃S-PPO (25 mol %)³181 283 287 13 CH₃SO₂-PPO (25 mol %)⁴ 211 332 339 15 CH₃SO₂-PPO (50 mol%)⁵ 228 327 336 16 CH₃SO₂-PPO (80 mol %)⁵ 262 331 340 wherein ¹T_(g) wasmeasured from mid-point of change in slope on DSC thermogram obtainedwith a heating rate of 10° C./min, ²temperature at which 5% weight lossrecorded on TGA thermogram obtained with a heating rate of 10° C./min,³prepared from Br-PPO (Example 1), ⁴prepared from CH₃S-PPO (Example 12)via m-CPBA oxidation and nearly identical thermal properties wereobserved for CH₃SO₂-PPO prepared by nucleophilic substitution of Br-PPO(25 mol %) with sodium methanesulfinate, and ⁵prepared from therespective Br-PPO via nucleophilic substitution with sodiummethanesulfinate.

In order to evaluate the suitability of the RSO₂-PPO films for use ashigh energy density capacitors, the dielectric properties of the filmswere determined using broadband dielectric spectroscopy (“BDS”) anddielectric displacement-electric field (D-E) loop measurements. BDSmeasurements of the γ transition reveal how much dipole switchingcontributes to the dielectric constant. Dipole switching only becomesactive at and above the γ transition temperature. D-E loop measurementswere used to investigate the high field performance of the CH₃SO₂-PPOfilms, to measure the dielectric constant at high field strengths, toestimate lossiness of the material based on the hysteresis, and todetermine the breakdown strength. Discharge energy and efficiency weredetermined from D-E loop data.

In order to determine the dielectric properties of the polymer samples,the samples were dried in a vacuum oven for 24 hr at 130° C. The sampleswere then silver coated (100 nm), on both sides, by physical vapordeposition to improve electrical contact. The coated samples were keptin a desiccator filled with desiccant until measurements were performed.

BDS measurements were carried out on a broadband dielectricspectrometer. Prior to measurements, a 38 μm thick film was coated, onboth sides, with 200 nm thin layers of aluminum and silver to improveelectrical contact. The temperature of the sample was programmed tochange linearly −140° C. to 150° C., at a rate of 2° C./min. The BDSspectrometer applied a set of sinusoidal voltages of 1 V rms from 107 Hzto 1 Hz across a sample film every 14 sec during the temperature rampingand recorded the resulting current. Similarly, the aluminum-coatedsample films were used in D-E loop measurements performed at 23° C.,100° C., and 190° C. The D-E loops were measured with a ferroelectricanalyzer by applying two consecutive sine waves of equal amplitudes andeach of 1000 Hz to the sample. The peak amplitude of the voltage wasincreased every two cycles beginning from field strengths of 50 MV/m andwith 316 MV/m. The results of the dielectric measurements are summarizedand compared with a current standard for polymer dielectrics, i.e.,biaxially oriented polypropylene (“BOPP”) in Table 4.

TABLE 4 Maxima Released Breakdown ∈_(r)′ ∈_(r)″ tan δ Energy Field (1kHz, (1 kHz, (1 kHz, Density Strength Sample ID 25° C.) 25° C.) 25° C.)(J/cm²) (MV/m) BOPP 2.2 0.0002 4.8 730 PPO 2.7-2.8 <0.028 <0.001 PPO-SMe3.5 0.01 0.0028 * * 25 mol % PPO-SO₂Me 6.0 0.06 0.008 30 (at 900 (25 mol%) 200 MV/m) PPO-SO₂Me 8.0 0.065 0.008 28 (at 800 (50 mol %) 240 MV/m)PPO-SO₂Me ~8.0* * * * * (80 mol %) wherein an asterisk, *, indicatespoor film quality.

FIGS. 4A and 4B include present BDS spectra of real ε_(r)′ and imaginaryε_(r)″ parts of permittivity as a function of temperature at differentfrequencies for 25 mol % CH₃SO₂-PPO (Example 13). One obvious transitioncould be identified between −140 and 150° C. with an electric field at100 Hz, that is, at about −90° C. Above −90° C., ε_(r)′ reached a peakvalue of 6.0. The foregoing transition may be assigned as a γ transitionresulting from the rotation of the sulfone groups, which can not onlyincrease dielectric constant, but also maintain a dielectric loss as lowas ε_(r)″=0.02. There was a slight decrease in ε_(r)′ starting fromabout 0° C. The slight decrease in ε_(r)′ may be due to the fact that astemperature increases, dipoles gained more thermal energy and theamplitude of random thermal motion increases, which reducesorientational polarization to some extent. With temperature increasingto around 70° C., a weak transition was observed in the spectrum of FIG.4B, which may be assigned as a weak β transition associated with thewaggling of ether groups along a polymer backbone. When temperaturesreached above 100° C., ε_(r)″ started to increase, likely resulting froma combination of dissipation caused by absorbed moisture and impurityions in the polymer matrix. While even 25 mol % CH₃SO₂-PPO (Example 13)demonstrated strong dipoles, CH₃SO₂-PPO was not sensitive to moistureand was capable of keeping a low dielectric loss up to 150° C. Theseproperties are very attractive for practical dielectric applications.

High-field dielectric properties were explored by D-E hysteresis loopmeasurements. At room temperature and at 1000 Hz, 25 mol % CH₃SO₂-PPO(Example 13) exhibited narrow bipolar linear loops at different electricfields ranging from 105 MV/m to 650 MV/m, as shown in FIG. 5A. Theapparent k was determined to be 6.2 via k=D/(e₀E), which was consistentwith the result obtained from BDS data. The linear nature of the loopssuggests that sulfonyl groups rotated easily without dipole couplingunder a high electric field. When the electric field was furtherincreased, such as to 800 MV/m, dielectric loss became noticeable(measured by the enclosed area inside the unipolar loops in FIG. 5B).The degree of dielectric loss increased with field because of eitherincreased ionic conduction or electronic conduction at high field. Atthe highest testing field (25 mol %), the dielectric of CH₃SO₂-PPO(Example 13) reached as high as 913 MV/m, above which breakdownoccurred. Such high breakdown strength may be attributed to: (1) therigid PPO backbone containing aromatic rings suppressed segmental motionand thus weakened charge hopping or tunneling under a high electricfield; (2) the coulombic interaction between dipoles and charge carrierscaused extra scattering in addition to phonon-electron scattering, whichreduced the conduction current and prevented dielectric breakdown bystabilizing the electron energy; (3) the polar groups served as traps ofcharge carriers; and (4) a uniform film with a smooth film surfacelowers surface-defects levels.

The discharge energy density (U_(e,discharged)) and discharge efficiencywere calculated from the electric displacement-electric field (D-E)loops and the plots for 25 mol % CH₃SO₂-PPO (Example 13) and 50 mol %CH₃SO₂-PPO (Example 15) provided in FIGS. 5 and 6, respectively. Withincreasing external electric field, U_(e,discharged) exponentiallyincreased up to 22 J/cm³ and 24 J/cm³ for 25 mol % CH₃SO₂-PPO (Example13) and 50 mol % CH₃SO₂-PPO (Example 15), respectively. The dischargeenergy density, U_(e,discharged) of 50 mol % CH₃SO₂-PPO (Example 15)increased faster than 25 mol % CH₃SO₂-PPO (Example 13), likely because50 mol % CH₃SO₂-PPO (Example 15) has a higher dielectric constant.However, 25 mol % CH₃SO₂-PPO (Example 13) exhibited lower dielectricloss and higher discharge efficiency (defined as 100(1−U_(e,discharged)/U_(e,stored))%). For example, upon exposure to anelectric field of 805 MV/m, 25 mol % CH₃SO₂-PPO (Example 13) had aU_(e,discharged) of 18 J/cm³ and a relatively high discharge efficiencyabout 91% (see FIG. 5B). The discharge efficiency of 50 mol % CH₃SO₂-PPO(Example 15) at about 635 MV/m was about 85% and dramatically decreasedwith increased the electric field, as shown in FIG. 6B. These resultssuggested higher dielectric constant and higher loss with increasingamounts of sulfonyl dipoles. Accordingly, increasing the amount ofsulfone groups attached on the side chain of the polymer may notnecessarily result in a better dipolar glass polymer.

While the present invention has been illustrated by a description of oneor more embodiments thereof and while these embodiments have beendescribed in considerable detail, they are not intended to restrict orin any way limit the scope of the appended claims to such detail.Additional advantages and modifications will readily appear to thoseskilled in the art. The invention in its broader aspects is thereforenot limited to the specific details, representative apparatus andmethod, and illustrative examples shown and described. Accordingly,departures may be made from such details without departing from thescope of the general inventive concept.

What is claimed is:
 1. A sulfone-containing polyphenylene oxide (PPO)polymer having repeating units of formulas:

wherein each of R¹ and R² is H or an alkyl group containing from 1 to 4carbon atoms, R³ is an alkylene group containing from 1 to 2 carbonatoms, R⁴ is selected from a group consisting of an alkyl groupcontaining from 1 to 4 carbon atoms, an aryl group, and CF₃, and X is ahalogen atom; the subscript n is 0 or 1; the subscript m is 1 or 2,provided that when m is 2, R² is H; a degree of polymerization rangesfrom about 5 to about 1,000; and a ratio of units having formula (1) tounits having formula (2) of the sulfone-containing PPO polymer rangesfrom about 10:90 to about 90:10.
 2. The sulfone-containing PPO polymerof claim 1, wherein X is Br.
 3. The sulfone-containing PPO polymer ofclaim 1, wherein R¹ is —CH₃ or —CH₂CH₃.
 4. The sulfone-containing PPOpolymer of claim 1, wherein R³ is —CH₂— or —CH₂CH₂— and R⁴ is CF₃. 5.The sulfone-containing PPO polymer of claim 1, wherein R³ is —CH₂— or—CH₂CH₂— and R⁴ is an aryl group.
 6. The sulfone-containing PPO polymerof claim 5, wherein the aryl group includes one, two, or threesubstituents selected from the group consisting of —CH₃, —OCH₃, adimethyl amino group, and a diethylamino group.
 7. Thesulfone-containing PPO polymer of claim 6, wherein the aryl group is apara-substituted aryl group and the substituent is selected from thegroup consisting of a halide, —CH₃, —OCH₃, a dimethyl amino group, and adiethylamino group.
 8. The sulfone-containing PPO polymer of claim 6,wherein the aryl group is an ortho-substituted aryl group and thesubstituent is selected from the group consisting of a halide, —CH₃,—OCH₃, a dimethyl amino group, and a diethylamino group.
 9. Thesulfone-containing PPO polymer of claim 6, wherein the aryl groupcomprises one para-group and two ortho-groups, each of the ortho-groupsis selected from the group consisting of —CH₃, —OCH₃, a dimethyl aminogroup, and a diethylamino group.
 10. The sulfone-containing PPO polymerof claim 1, wherein an amount of halogen-containing units in the polymerranges from about 0.2 mol % to about 0.4 mol %.
 11. Thesulfone-containing PPO polymer of claim 1, wherein units of formula (1)comprise units of formulas:

wherein a molar ratio of units of formula (3) to units of formula (4)ranges from about 64:36 to about 99:1.
 12. The sulfone-containing PPOpolymer of claim 1, wherein units of formula (2) comprise units offormulas:

wherein a molar ratio of units of formula (5) to units of formula (6)ranges from about 1:0 to about 5:3.